Polymerized chloroprene compositions



Patented Aug. 31, 1943 rotmarzan CHLOROPRENE comosrrrons Alexander D. MacDonald, Maiden, Mass, assignor to B. B. Chemical 60., Boston, Man, a corporation of Massachusetts No Drawing. Application January 31, 1940, Serial No. 316,513

6 Claims.

,This invention relates to polymerized chloroprene and more particularly to liquid compositions prepared from malodorant-free plastic polymers of chloroprene.

Plastic polymerized chloroprene is chloroprene (also known as chloro-2-butadiene-1,3) which has been polymerized to such an extent that it may be worked on the rolls of a rubber mill and compounded with other ingredients in a manner similar to that in which crude rubber is treated. Such plastic polymerized chloroprene may be "cured to a condition in which it resembles vulcanized rubber in exhibiting essentially elastic rather than plastic properties. This curing of plastic polymerized chloroprene, often spoken of as vulcanization, appears to be a further polymerization of the chloroprene as distlnguished from the vulcanization of rubber wherein sulphur is considered to be added to the molecule of the rubber hydrocarbon. V

For many purposes the malodorant character of commercial polymerized chloroprene was disadvantageous and to overcome this difficulty I made the inventions described in United States Letters Patent Nos. 2,067,854 and 2,107,796, which are directed to the preparation of malodorantfree plastic polymerized chloroprene from commercial polymerized chloroprene. The present invention makes it possible to prepare in advance liquid dispersions of malodorant-free plastic polymerized chloroprene which will retain their liquidity and free-flowing qualities for substantial periods of time and, when occasion requires, they may quickly be associated with suitable compounding ingredients, including curing agents, depending upon the particular use to 'which the liquid dispersions are to be put.

An object of this invention is to provide improved liquid compositions embodying malodorant-free plastic polymerized chloroprene. Other objects are to provide such compositions having improved stability, that is, increased resistance to thickening and gelling over a period of time, and which may be stored for substantial periods of time without deterioration.

According to the present invention the above and other objects are attained by incorporating "alkali" (that is, sodium, potassium, ammonium) salts of certain oxygen-containing acids in the dispersion or colloidal solution of plastic polymerized chloroprene. Compositions so treated have stood at temperatures as high as 105 F. for many weeks without gelling or undue thickening, whereas compositions containing no stabilizing materials have increased greatly in viscosity and actually gelled in much shorter periods of time.

I have found that the oxygen-containing acids, the alkali salts of which produce the results contemplated by this invention, fall within the group consisting of acids containing oxygen and sulphur, inorganic acids containing oxygen and phosphorus, and alkanoic acids (CnH2n+lCOOH series). Examples of "alkali" salts of acids containing oxygen and sulphur in the form of a sulphur-oxygen group are sodium sulphate (NazsOi), sodium bisulphate (NaHSOr), sodium thiosulphate (NazSzOs), potassium acid sulphate (EH04), ammonium bisulphate (NHiHSOi), sodium bisulphite (NaHSOa) sodium hydrosulphite (NazszOi), potassium metabisulph'ite (KzSzOs), sodium sulphanilate, (CsH4(NHz)SO2ONa). Examples of alkali salts of inorganic acids containing oxygen and phosphorus are sodium monobasic phosphate (NaHzPol), sodium phosphite (Nazi-IP03). Examples of alkali salts of alkanoic acids are sodium formate (HCOONa), sodium acetate (NaCzHaOz), sodium stearate (CuHaaCOONa). Of the group of alkali salts of alkanoic acids I have found sodium acetate to be especially useful because of its availability, low cost and effectiveness. I

The alkali salt of the oxygen-containing acid 7 of the group described above preferably is present in the composition to the extent of about 1 to 10% by weight of the polymerized chloroprene present. I have found that about 3% of thea-lkali salt functions very satisfactorily.

I have conducted aging tests of liquid dispersions made in accordance with this invention, the results of which are given hereinbelow. I selected F. as the temperature at which to conduct these tests, because liquid dispersions of polymerized chloroprene ordinarily are less stable at elevated temperatures, and 105 F. represents the maximum temperature at which such dispersions ordinarilly would be stored. In these tests dispersions in toluene of malodorant-free plastic polymerized chloroprene, which had been deodorized in the manner described in Patent No. 2,067,854, were prepared with a concentration of about 2 pounds of the polymerized chloroprene to the gallon of solution. In each case 3% of the alkali salt was incorporated in the liquid composition. These compositions were then stored in a constant temperature chamber at 105 F. The following table illustrates .the efficacy of certain of the alkali salts coming within the scope of this invention and shows the viscosity of the solutionsat the beginning of the test and after 8 weeks constant exposure to a colloidal dispersions.

temperature of 105 F. except where the composition had gelled prior to the expiration of the 8 weeks period.

Viscosity or iifitfii Alkali salt cnmgosmon weeks at i f 105 F mug es (Seconds) (seconds) None 27% Sodium sulphate (Nelson 24 46 Sodium bisulphate (NaHSOO a 17 22 Sodium tliiosuiphntc (Na S Oa) 18 18 Potassium acid sulphate (KHSO 26 32 Ammonium bisulphate (NH4HSO4 26 37 Sodium bisulphite (NaHSOa) 20% 33% Sodium hydrosulphite (No seoi). 27 32 Potassium metahisulpliite (K;1 S 0 21% 40 Sodium sulphanilnte (CqHKNHg) SOQONB) 27 36 Sodium monobasic phosphate (NaHQPOl). 24 36 Sodium phosphite (Na HP03).. V 28 40% Sodium iorinuto (HCOONa) 25 63 Sodium acetate (NHCZHQOZ) 21 36%; Sodium stearato (CI7H35COONB) 26 72 1 Gelled after 6 weeks.

The viscosity mentioned hereinabove refers to the number of seconds required for a steel ball of 9,5 mm. diameter) and weighing from 3.45 to 3.55 grams to drop 50 cm. through a sample a .of the liquid maintained at 25 C. in a glass tube of 19 mm. inside diameter.

From the above test results it will be observed that while ordinarily there was a relatively small increase of viscosity such increase is well within the limits normally to be expected from such The above compositions after storage were all suitable for the uses to -which such compositions ordinarily are put.

Jrhe alkali salt of the oxygen-containing acid may be incorporated in the polymerized chloroprene dispersion in any suitable manner. Thus, the alkali salt in finely powdered state may be milled into the polymerized chloroprene on a suitable rubber mill. The milled material then may be sheeted, cut up into relatively small pieces, and dissolved in a suitable solvent, such as benzene, trichlorethylene, toluene, Solvesso, alone or in mixtures, or the solvent may be associated with a non-solvent such as ethyl acetate or naphtha.

"Alternatively, the polymerized chloroprene may ingredients of the type well known in the art may be incorporated in the liquid dispersion.

Having described my invention, what I claim as new and desire to secure by Letters Patent of the United States is:

,1'. A liquid composition comprising malodorantfree plastic polymerized chloroprene dispersed in an organic solvent, said composition being characterized by resistance to thickening and gelling over a substantial period of time and by the presence therein of an alkali salt, selected from the group of sodium, potassium, and ammonium salts, of an inorganic acid containing a sulphur-oxygen 2. A liquid composition comprising malodorantfree plastic polymerized chloroprene dispersed in an organic solvent, said composition being characterized by resistance to thickening and gelling over a substantial period of time and, by the presence therein of about 1 to 10% of a sodium salt of an inorganic acid containing a sulphuroxygen group.

3. A liquid composition comprising malodorantfree plastic polymerized chloroprene dispersed in an organic solvent, said composition being characterized by resistance to thickening and gelling over a substantial period of time and by the presence therein of about 3% of a sodium salt of an inorganic acid containing a sulphur-oxygen group.

4. A liquid composition comprising malodorantfree plastic polymerized chloroprene dispersed in an organic solvent, said composition being characterized by resistance to thickening and gelling over a substantial period of time and by the pres: ence therein of about 1 to 10% of an alkali salt of the group consisting of sodium sulphate (NaZSOi), sodium bisulphate (NaHSOO, sodium thiosulphate (NazSzOs), potassium acid sulphate (KHSO4) ammonium bisulphate (NH4HSO4), sodium bisulphite (NaHSOz), sodium hydro'sulphite (Na2SzO4), and potassium metabisulphite (K2S205).

5. A liquid composition comprising malodorantfree plastic polymerized chloroprene dispersed in an organic solvent, said composition being characterized by resistance to thickening and gelling over a substantial period of time and by the presence therein of about 3%, of sodium bisulphite (NaHSOs).

6. The method of inhibiting thickening and gelling of a liquid dispersion of malodorant-free plastic polymerized chloroprene which comprises incorporating in said dispersion an alkali salt, selected from the group of sodium, potassium, and ammonium salts of an inorganic acid containing a sulphur-oxygen group.

ALEXANDER D. MACDONALD.

CERTIFICATE OF comc'rion. Patent No. 2,52 ,551. August 51, 1915.

AIEXANDER D. MACDONALD.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, sec- 0nd column, line 15, for "(KHO Y' read -(KHSO end that the seid Lettars Patent should. be read with'this "correction therein that the same may conform to the record of the case in the Patent Ofijice.

si ned and sealed this 2nd day of November, A. D. 1915.

Henry Van Arsdele, (Seal) Acting Commissioner of Patents. 

